US6479620B1 - Process for converting caprolactam to nylon 6 - Google Patents

Process for converting caprolactam to nylon 6 Download PDF

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Publication number
US6479620B1
US6479620B1 US09/872,288 US87228801A US6479620B1 US 6479620 B1 US6479620 B1 US 6479620B1 US 87228801 A US87228801 A US 87228801A US 6479620 B1 US6479620 B1 US 6479620B1
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Prior art keywords
column
stage
caprolactam
reactor
pressure
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US09/872,288
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English (en)
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US20020183478A1 (en
Inventor
Stuart B. Fergusson
Ernest Keith Marchildon
Ahmet Turgut Mutel
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Invista North America LLC
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EI Du Pont de Nemours and Co
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Priority to US09/872,288 priority Critical patent/US6479620B1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MARCHILDON, ERNEST KEITH, MUTEL, AHMET TURGUT, FERGUSSON, STUART B.
Priority to TW091111076A priority patent/TWI254723B/zh
Priority to CZ20033072A priority patent/CZ297824B6/cs
Priority to PCT/US2002/021072 priority patent/WO2002102876A2/en
Priority to EA200301327A priority patent/EA004901B1/ru
Priority to KR1020037015552A priority patent/KR100785985B1/ko
Priority to BRPI0210053-3A priority patent/BR0210053B1/pt
Priority to PL02364555A priority patent/PL364555A1/xx
Priority to SK1428-2003A priority patent/SK14282003A3/sk
Priority to MXPA03010922A priority patent/MXPA03010922A/es
Priority to CNB028110773A priority patent/CN1249124C/zh
Priority to GE5404A priority patent/GEP20063776B/en
Priority to DE60209746T priority patent/DE60209746T2/de
Priority to CA002447492A priority patent/CA2447492C/en
Priority to EP02756371A priority patent/EP1392758B1/en
Priority to JP2003506345A priority patent/JP3984224B2/ja
Priority to MYPI20022029A priority patent/MY127581A/en
Publication of US6479620B1 publication Critical patent/US6479620B1/en
Application granted granted Critical
Publication of US20020183478A1 publication Critical patent/US20020183478A1/en
Priority to ZA200308138A priority patent/ZA200308138B/en
Assigned to INVISTA NORTH AMERICA S.A.R.L. reassignment INVISTA NORTH AMERICA S.A.R.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: E. I. DU PONT DE NEMOURS AND COMPANY
Assigned to JPMORGAN CHASE BANK, N.A. reassignment JPMORGAN CHASE BANK, N.A. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INVISTA NORTH AMERICA S.A.R.L. F/K/A ARTEVA NORTH AMERICA S.A.R.
Assigned to DEUTSCHE BANK AG NEW YORK BRANCH, AS COLLATERAL AGENT reassignment DEUTSCHE BANK AG NEW YORK BRANCH, AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: INVISTA NORTH AMERICA S.A.R.L.
Assigned to INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH AMERICA S.A.R.L.) reassignment INVISTA NORTH AMERICA S.A.R.L. (F/K/A ARTEVA NORTH AMERICA S.A.R.L.) RELEASE OF U.S. PATENT SECURITY INTEREST Assignors: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT (F/K/A JPMORGAN CHASE BANK)
Assigned to INVISTA NORTH AMERICA S.A.R.L. reassignment INVISTA NORTH AMERICA S.A.R.L. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: DEUTSCHE BANK AG NEW YORK BRANCH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention concerns a process for the conversion of caprolactam to nylon-6.
  • Nylon-6 is produced commercially using caprolactam as the starting material.
  • a commercial process typically involves heating caprolactam in a VK tube at atmospheric pressure for 12 to 24 hours. This process produces a nylon-6 product that contains 7 to 10% caprolactam in the product. Excess caprolactam is extracted using an 8 to 12 hour aqueous extraction process. The extracted product is then dried for 8 to 12 hours producing a dry product containing 0.2 to 0.3% caprolactam. While this process has met with commercial success, it has a long reaction residence time and a slow extraction/drying step.
  • U.S. Pat. No. 6,201,096 discloses a process for the production of a polyamide by reaction of an omega-aminonitrile with water in a vertical multistage reactor that is swept by steam. For example, this process can convert 6-aminocapronitrile to nylon-6.
  • the present invention is a process for making nylon-6, comprising:
  • the process is expected to involve relatively short holdup times for the conversion of caprolactam to nylon-6. It is also expected to produce nylon-6 with relatively low amounts of free caprolactam and/or other low molecular weight compounds.
  • FIGS. 1 and 3 are schematic views of apparatus that can be used to carry out the present invention.
  • FIGS. 2 and 2A are plan views of plates separating stages of the column reactor of the present invention.
  • FIGS. 4 and 5 are elevational views of the interior of stages in the column reactor of the present invention.
  • FIG. 5 is a sectional view of a stage taken along line V—V in FIG. 6 .
  • FIG. 6 is a sectional view of the interior of a stage taken along line VI—VI in FIG. 5 .
  • the process of the present invention is a continuous process for preparing nylon-6 by reaction of caprolactam in a countercurrent multistage column reactor.
  • An aqueous solution of caprolactam is first reacted in a pre-reactor under pressure to initiate (facilitate) ring opening reactions to convert a portion of caprolactam into linear aminocaproic acid.
  • the mixture from the pre-reactor is continuously fed to a countercurrent multistage reactor where the reaction mixture continues to react via both poly-condensation and poly-addition reactions to form a polyamide.
  • Unreacted caprolactam is continuously stripped from the polymeric mixture near the bottom of the reactor by steam flowing countercurrently to the reaction mixture and re-absorbed into the reaction mixture at the upper stages of the reactor.
  • a polyamide containing significantly less caprolactam than the equilibrium value dictated by the poly-addition reaction should be produced at shorter residence times than conventional reactors due to the counter-current steam stripping and subsequent internal caprolactam recycle.
  • caprolactam 25 and water 26 are first reacted at elevated temperature in a pre-reactor 200 to produce a product 28 that contains some linear aminocaproic acid.
  • the mole ratio of caprolactam to water is not critical, but preferably is about 0.4 to 0.6.
  • the pre-reactor temperature is maintained between 200 and 250 degrees C. and the pressure is between 100 and 300 psia (0.69 to 2.07 MPa), preferably between 150 and 200 psia (1.03 to 1.38 MPa).
  • a plug flow type reactor is preferred to achieve a narrow residence time distribution.
  • a tubular reactor or a column reactor can be used.
  • the column reactor is an up-flow packed reactor. Hold-up time for the pre-reactor is between 20 to 40 minutes, preferably 30 minutes.
  • the pre-reactor reaction product 28 is fed continuously near the top of a multistage column reactor 100 .
  • Standard distillation columns are suitable for use in the process of the current invention if the residence times in the stages are increased to give sufficient time for the reaction times required.
  • the required liquid residence time in the reactor is between four hours and eight hours to achieve the average molecular weights required for a commercially usable product.
  • the column reactor 100 is equipped with internals, such as, but not limited to, perforated plates 13 to 23 and an agitator assembly 31 , comprising a motor 31 A, a shaft 31 B, and agitiator blades 31 C. These internals should be configured to cause effective staged contact of the countercurrently flowing steam with the liquid reaction mixture to ensure that adequate mass transfer is achieved for effective stripping of the caprolactam and cyclic dimer, especially in the lower part of the column reactor.
  • the interior of the multistage reactor 100 is divided into discrete stages 1 to 12 using perforated plates 13 to 23 between the stages.
  • the plates shown in FIG. 2 (and FIG. 2 A), include small perforations 36 ( 36 ′) which allow vapor to flow upward from stage to stage, and a larger downcomer tube (or tubes) 37 ( 37 ′) which leads from each stage into and below the surface of the reaction mixture in the stage below, allowing the liquid to flow downward from stage to stage.
  • a flooded tray configuration is preferred in the bottom stages where agitation is employed to achieve good mixing and improved mass transfer.
  • the shaft 31 B for the agitator blades 31 C should easily extend through the concentric downcomers 37 .
  • Stages where no agitation is required can be any type of tray configuration employed in distillation equipment, such as flooded or weir trays but preferably with arrangements shown in FIGS. 4, 5 and 6 to minimize any liquid back flow due to vapor traffic in the column and to provide adequate mixing of the incoming liquid into each stage reaction mass.
  • the number of stages is chosen to achieve a high rate, per unit of liquid volume, of mass transfer and chemical reaction. Six to fifteen stages are typical.
  • the pre-reactor reaction product 28 is fed continuously near the top of the multistage column reactor 100 , and steam 30 is fed continuously to one or more of the bottom-most stages of the reactor.
  • a pressure control valve 27 is employed between the pre-reactor 200 and the column reactor 100 to maintain a higher pressure in the pre-reactor compared to that of the column reactor.
  • the steam can be saturated steam, steam containing a small amount of water, or superheated steam, with superheated steam being preferred in order to minimize the heating requirement within the reactor.
  • the steam is introduced into the reactor 100 at a weight flow rate that is at least 30 percent of and preferably approximately equal to the weight flow rate of the pre-reactor feed.
  • a vapor stream 34 is removed from the top of the column.
  • the stream 34 will contain steam and some caprolactam.
  • the caprolactam can be further separated and recycled to the column reactor 100 .
  • Polyamide product 24 is continuously removed from the bottom stage 1 using, for example, pump 38 .
  • the column reactor 100 preferably includes means to separate and return to the column any caprolactam which leaves the top part of the column as a vapor or as an entrained liquid.
  • One such means is a partial condenser 39 at the top of the column. By means of manipulating the flow and temperature of a cooling fluid into 32 and out of 33 the cooling side of the partial condenser 39 , the condenser is maintained at a temperature sufficient to condense and return most of the caprolactam to the column while allowing steam to be removed in vapor stream 34 .
  • the use of the partial condenser can control the temperature of the top stage 12 of the column reactor 100 . Further control of the temperature can be achieved by manipulation of the flow rate of water stream 26 to the pre-reactor. Additionally, one or more stages can be added to the column reactor above the feed stage, and a partial condenser (not shown) can be provided above the uppermost of these stages to provide reflux liquid.
  • the temperature in the column should be maintained sufficiently high that the reaction mixture does not freeze.
  • the temperature at the top stage 12 of the column is maintained at a lower temperature than the temperature at the bottom stage 1.
  • the top temperature is maintained at a temperature that is high enough to keep the reaction mixture in a liquid state, and condense most of the caprolactam in the vapor stream entering the stage from the stage below.
  • the temperature of the top stage of the column reactor 100 should be between 150 and 200 degrees C. It is possible to use a combination of upper stage 12 temperature and a partial condenser 39 to minimize outflow of caprolactam.
  • the temperature of bottom stage 1 is adjusted to be kept sufficiently above the melting point of the polyamide to keep the reaction mixture in a liquid state, but as low as possible to minimize the regeneration of caprolactam and cyclic dimer through a reverse polyaddition reaction.
  • the temperature of the bottom stage should be between 240 and 260 degrees C.
  • the ability to achieve a nylon-6 product with a free caprolactam content significantly lower than the equilibrium concentration depends on the cumulative difference between the removal of caprolactam from the reaction mixture by steam stripping and the generation of caprolactam by reverse reaction. This ability requires that the average temperature in the stages not exceed a value above which the regeneration rate of caprolactam becomes higher than the stripping rate by steam. Averaging over the bottom half of the reactor, this temperature is approximately between 240 to 260 degrees C.
  • stages 1 to 12 are preferably equipped with means for independent control of temperature. This control is best accomplished by use of a hot flowing liquid heat transfer medium passing through jackets, coils, or other heat-transfer devices 40 to 48 which can be used for both heating and cooling.
  • the column is operated at atmospheric or sub-atmospheric pressure, preferably less than 15 psia (0.10 MPa), more preferably between 6 and 8 psia (0.041 to 0.055 MPa) to achieve the desired low level of caprolactam in the product stream 24 .
  • the product should preferably contain less than 1%, most preferably less than 0.5% by weight free caprolactam to minimize or eliminate the need for water extraction.
  • the pressure can be controlled by means of a pressure control valve 35 and a vacuum system (not shown), like annular steam vacuum jets or vacuum pumps. Pressure control valve 35 is continuously adjusted to vary the outflow of vapor stream 34 in response to the measured pressure in the vessel.
  • the main advantage of the process of the present invention is expected to be that the countercurrent operation of the column will result in continual stripping of caprolactam from the lower parts of the column reactor, with high conversion, and re-condensing it at the upper parts, with low conversion, so that a nylon-6 product with low free caprolactam content is achieved.
  • Steam is injected into the vapor space in the stages, preferably by use of a gas distributor to achieve a uniform distribution. Steam is preferably injected into the liquid zone in the bottom stage 1 to maximize the mass transfer efficiency in this stage. This can be accomplished by the use of a gas distributor which has high pressure drop nozzles to avoid nozzle pluggage and provide uniform gas distribution.
  • a mixer assembly 31 is preferably used in one or more of the bottom-most stages in the reactor. In the reactor shown in FIG. 1, mechanical mixing is provided in the bottom four stages by use of agitator blades 31 C.
  • mixing within each stage is achieved by either proper arrangement of heating coils 46 to 48 to assist gas induced mixing or by mechanical agitation in the lower stages. Insufficient mixing reduces the desired reaction efficiency, resulting in a requirement for a larger size column reactor to achieve the same caprolactam to nylon 6 conversion at a given flow rate. Height-to-diameter ratio for each stage is preferably between 0.5 to 1.2 to achieve the desired mixing efficiency.
  • Axial mixing between the stages in the column reactor (as a result of liquid backflow through the downcomers induced by large bubbles either entering the downcomers or forcing liquid into the downcomers as they approach the downcomers) will reduce the overall efficiency in the column reactor.
  • the following preferred arrangements of downcomers can be employed in the column reactor 100 to reduce axial mixing.
  • FIG. 4 there is shown the internal arrangement of a stage such as stage 9 of the column reactor 100 .
  • the stage contains a continuous liquid portion 60 (from the bottom of the stage to the level indicated by reference numeral 61 ) and a continuous vapor portion 62 .
  • coils 45 for heating or cooling the stage.
  • the arrow indicated as “B” shows the movement of the liquid around the coils 45 caused by the bubbles 52 .
  • the stage contains a circular central downcomer 50 , which preferably has a bi-conical attachment 51 at the bottom to (1) deflect the gas bubbles 52 away from the downcomer, (2) prevent gas bubbles entering the downcomer, and (3) deflect the liquid exiting the downcomer (shown by the arrow indicated as “A”).
  • the gap between the attachment 51 and the bottom of the downcomer 50 is needed to minimize liquid backflow in the downcomer induced by the pressure field created by the gas bubbles travelling near the downcomer exit.
  • the gap is adjusted such that the pressure drop created by the liquid flow is between 0.5 to 1.0 inches of liquid.
  • At the bottom of the stage are downcomers 55 that allow liquid to flow into the next lower stage, such as that shown in FIG. 5 .
  • Another preferred arrangement involves multiple downcomers 55 arranged in a triangular pattern, as illustrated in FIG. 5 .
  • the bottoms of these downcomers 55 are truncated at an angle between 30 and 60 degrees with welded, extended ellipsoidal plates 56 to deflect gas bubbles. Liquid is allowed to exit through a rectangular slit protected by the extended plate and pressure dissipating attachment. Slit dimensions are arranged to provide a pressure drop between 0.5 inches and 1.0 inch liquid to minimize backflow.
  • the preferred arrangement of downcomers 50 and 55 with respect to each other is shown in FIG. 6 to achieve a maximum mixing efficiency in the stage.
  • the reactor stages are configured as flooded trays to allow an agitator shaft 31 B to pass through the downcomers (not illustrated) to avoid sealing the rotating shaft against liquid.
  • mechanical mixing is required at the bottom four stages of the reactor to minimize liquid by-pass. In these stages mixing induced by gas traffic (as indicated by the flow arrows in FIG. 4) may not be sufficient to achieve the desired quality of mixing at higher viscosities.
  • flooded trays are still preferred, because they allow reactor level control to be achieved by measurement at the uppermost stage where it is most convenient.
  • the polyamide product 24 removed from the bottom of the column is expected to generally have a number average molecular weight between 13,000 and 17,000 and a relative viscosity (RV) between about 35 and 55.
  • the polyamide product is expected to contain water extractable compounds, such as caprolactam, at less than 1% by weight and cyclic dimer less than 0.5% by weight.
  • the polyamide product 24 is continuously removed from the bottom of the reactor by means of a pump 38 and can be pelletized using methods known in the art, such as strand casting.
  • Polyamide 6 pellets of number average molecular weight approximately 16,000 were melted in the apparatus, and steam was injected into the liquid in the bottom stage using various gas distributors. Polymer was melted with steam injection at different steam-to-polymer ratios, including no steam injection, to confirm the extractables regeneration rates. Polymer and condensate samples were collected at regular intervals and analyzed for extractables content to determine the mass transfer coefficients. Mass transfer coefficients and kinetic rates determined with those lab experiments were included in the mathematical models to generate the example presented below.
  • a counter-current column with 12 stages was simulated using the mathematical model, with a pre-reactor operating at 150 psia (1.03 MPa) and 220 degrees C.
  • a caprolactam solution containing 17% water by weight is fed to the pre-reactor at a rate of 172 lb/hr.
  • Pre-reactor was chosen to have a 30 minute hold-up time under these conditions.
  • Reaction mixture from the pre-reactor is predicted to contain 49.6% caprolactam by weight, 10% residual water by weight, remainder being a polymeric mixture with a degree of polymerization of 14. This mixture is continuously fed to the top stage of the reactor which is maintained at 160 C.
  • Superheated steam is injected at the bottom stage of the reactor at a rate of 80 lb/hr.
  • the bottom one-third of the reactor is maintained at 240 C.
  • Stage temperatures for the upper one third of the column are allowed to reach adiabatic conditions.
  • Column pressure is controlled at 7.5 psia (0.052
  • a vapor is expected to leave the top stage entering the partial condenser at a rate of 126 lb/hr. This vapor is predicted to contain 22% by weight caprolactam and 78% by weight steam.
  • a polymer product from the bottom of the reactor is predicted to be produced at a rate of 125 lb/hr, and to have a number average molecular weight of 17700 (55 RV). The polymer product is predicted to contain 0.3% caprolactam, 0.27% cyclic dimer and 0.2% water. Total residence time in the column reactor is predicted to be six hours.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US09/872,288 2001-06-01 2001-06-01 Process for converting caprolactam to nylon 6 Expired - Lifetime US6479620B1 (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
US09/872,288 US6479620B1 (en) 2001-06-01 2001-06-01 Process for converting caprolactam to nylon 6
TW091111076A TWI254723B (en) 2001-06-01 2002-05-24 Process for converting caprolactam to nylon 6
DE60209746T DE60209746T2 (de) 2001-06-01 2002-05-29 Verfahren zur umsetzung von caprolactam zu nylon 6
JP2003506345A JP3984224B2 (ja) 2001-06-01 2002-05-29 カプロラクタムをナイロン６に変換する方法
EA200301327A EA004901B1 (ru) 2001-06-01 2002-05-29 Способ получения найлона-6
KR1020037015552A KR100785985B1 (ko) 2001-06-01 2002-05-29 카프로락탐을 나일론 6으로 전환시키는 방법
BRPI0210053-3A BR0210053B1 (pt) 2001-06-01 2002-05-29 processo de fabricação de nylon-6.
PL02364555A PL364555A1 (en) 2001-06-01 2002-05-29 Process for converting caprolactam to nylon 6
SK1428-2003A SK14282003A3 (sk) 2001-06-01 2002-05-29 Spôsob konverzie kaprolaktámu na nylon 6
MXPA03010922A MXPA03010922A (es) 2001-06-01 2002-05-29 Proceso para convertir caprolactama a nylon 6.
CNB028110773A CN1249124C (zh) 2001-06-01 2002-05-29 将己内酰胺转化成尼龙－6的方法
GE5404A GEP20063776B (en) 2001-06-01 2002-05-29 Process for Converting Caprolactam to Nylon 6
CZ20033072A CZ297824B6 (cs) 2001-06-01 2002-05-29 Zpusob konverze kaprolaktamu na nylon 6
CA002447492A CA2447492C (en) 2001-06-01 2002-05-29 Process for converting caprolactam to nylon 6
EP02756371A EP1392758B1 (en) 2001-06-01 2002-05-29 Process for converting caprolactam to nylon 6
PCT/US2002/021072 WO2002102876A2 (en) 2001-06-01 2002-05-29 Process for converting caprolactam to nylon 6
MYPI20022029A MY127581A (en) 2001-06-01 2002-05-31 Process for converting caprolactam to nylon 6
ZA200308138A ZA200308138B (en) 2001-06-01 2003-10-20 Process for converting caprolactam to nylon 6.

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Application Number Priority Date Filing Date Title
US09/872,288 US6479620B1 (en) 2001-06-01 2001-06-01 Process for converting caprolactam to nylon 6

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US6479620B1 true US6479620B1 (en) 2002-11-12
US20020183478A1 US20020183478A1 (en) 2002-12-05

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US (1) US6479620B1 (es)
EP (1) EP1392758B1 (es)
JP (1) JP3984224B2 (es)
KR (1) KR100785985B1 (es)
CN (1) CN1249124C (es)
BR (1) BR0210053B1 (es)
CA (1) CA2447492C (es)
CZ (1) CZ297824B6 (es)
DE (1) DE60209746T2 (es)
EA (1) EA004901B1 (es)
GE (1) GEP20063776B (es)
MX (1) MXPA03010922A (es)
MY (1) MY127581A (es)
PL (1) PL364555A1 (es)
SK (1) SK14282003A3 (es)
TW (1) TWI254723B (es)
WO (1) WO2002102876A2 (es)
ZA (1) ZA200308138B (es)

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WO2004085512A1 (de) * 2003-03-26 2004-10-07 Basf Aktiengesellschaft Verfahren zur herstellung von polyamiden
US20110196093A1 (en) * 2010-02-11 2011-08-11 Basf Se Method of forming a polyamide
US20130131306A1 (en) * 2010-06-16 2013-05-23 Bioamber S.A.S. Processes for producing caprolactam and derivatives thereof from fermentation broths containing diammonium adipate or monoammonium adipate
CN104213240A (zh) * 2014-09-18 2014-12-17 海安县华荣化纤有限公司 一种耐热抗氧化的尼龙6化纤的制备方法

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BRPI0602511A (pt) * 2006-07-05 2008-02-26 Etruria Ind De Fibras E Fios S reator e processo para produção de biodiesel
US9073867B2 (en) 2011-04-09 2015-07-07 Amyris, Inc. Process for preparing caprolactam and polyamides therefrom
BR112014020642B1 (pt) * 2012-02-23 2020-12-29 Archer-Daniels-Midland Company processos para a preparação de um produto de caprolactama, para produzir nylon 6 e para a produção de caprolactama a partir de ácido adípico
US9708271B2 (en) 2012-11-06 2017-07-18 Uhde Inventa-Fischer Gmbh Extraction reactor and also method for extraction from granular material
ES2747448T3 (es) * 2012-11-06 2020-03-10 Uhde Inventa Fischer Gmbh Reactor de extracción así como procedimiento para la extracción de material granular
PL2784102T3 (pl) * 2013-03-26 2016-06-30 Uhde Inventa Fischer Gmbh Sposób i urządzenie do ciągłej recyrkulacji wód ekstrakcyjnych w procesie produkcji poliamidu
WO2015060829A1 (en) * 2013-10-22 2015-04-30 Empire Technology Development Llc Compounds and methods for producing nylon 6
WO2015060827A1 (en) 2013-10-22 2015-04-30 Empire Technology Development Llc Methods and compounds for producing nylon 6,6
CN105658616A (zh) 2013-10-25 2016-06-08 英派尔科技开发有限公司 产生二羰基化合物的方法
GB201320518D0 (en) * 2013-11-20 2014-01-01 Invista Tech Sarl Continuous polyamidation process - II
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